4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Femtosecond infrared (IR) pump probe and dynamic hole burning experiments were used to examine the ultrafast response of the modes in the 1600−1700 cm-1 region (the so-called amide I modes) of N-methylacetamide (NMA) and three small globular peptides, apamin, scyllatoxin, and bovine pancreatic trypsin inhibitor (BPTI). A value of 16 cm-1 was found for the anharmonicity of the amide I vibration. Vibrational relaxation of the amide I modes of all investigated peptides occurs in ca. 1.2 ps. An even faster value of 450 fs is obtained for NMA, a model for the peptide unit. The vibrational relaxation is dominated by intramolecular energy redistribution (IVR) and reflects an intrinsic property of the peptide group in any environment. Dynamic hole burning experiments with a narrow band pump pulse which selectively excites only a subset of the amide I eigenstates reveal that energy migration between different amide I states is slow compared with vibrational relaxation. Two-dimensional pump−probe (2D-IR) spectra th...

Structure of the amide i band of peptides measured by femtosecond nonlinear-infrared spectroscopy

This review is concerned with quantum confinement effects in low-dimensional semiconductor systems. The emphasis is on the optical properties, including luminescence, of nanometre-sized microcrysta...

Low-dimensional systems: quantum size effects and electronic properties of semiconductor microcrystallites (zero-dimensional systems) and some quasi-two-dimensional systems

This is a review and analysis of the optical properties of quantum crystallites, with principal emphasis on the electro-optic Stark effect and all optical third order nonlinearity. There are also introductory discussions on physical size regimes, crystallite synthesis, quantum confinement theory, and linear optical properties. The experiments describe CdSe crystallites, exhibiting strong confinement of electrons and holes, and CuCl crystallites, exhibiting weak confinement of the exciton center of mass. In the CdSe system, neither the Stark effect nor the third order nonlinearity is well understood. The Stark shifts appear to be smaller than calculated, and field inducted broadening also occurs. The third order nonlinearity is only modestly stronger than in bulk material, despite theoretical prediction. Unexpectedly large homogeneous widths, due to surface carrier trapping, in the nominally discrete crystallite excited states appear to be involved. The CuCl system shows far narrower spectroscopic homogeneous widths, and corresponds more closely to an ideal quantum dot in the weak confinement limit. CuCl also exhibits exciton superradiance at low temperature. Surface chemistry and crystallite encapsulation are critical in achieving the predicted large Stark and third order optical effects in II-VI and III-V crystallites.

Quantum crystallites and nonlinear optics

Generalized Bloch equations for laser-excited semiconductors are derived applying quantum-mechanical projection-operator techniques. The equations include phase-space filling and the many-body Coulomb effects. The coherent part of the equations is evaluated for the regime of ultrafast-pump-probe excitation and shown to reduce to the inhomogeneously broadened two-level Bloch equations for the different momentum states if the proper Coulomb enhancement in the density of states is taken into account. For the high-excitation quasithermal regime a generalization of the Elliott formula for the absorption spectrum is derived which is valid not only for bulk semiconductors, but also for quantum-well structures and other systems with reduced spatial dimensions.

Effective Bloch equations for semiconductors

The influence of the Coulomb interaction on one and two electron-hole-pair excitations in semiconductor quantum dots is analyzed. Using a numerical matrix-diagonalization scheme, the energy eigenvalues and the eigenfunctions of the relevant states are computed. Significant deviations from the strong-confinement approximation are observed. It is shown that the biexciton binding energy increases with decreasing dot size. This result is verified using third-order perturbation theory for small quantum dots. The optical properties of the quantum dots are computed, and it is shown that the Coulomb interaction significantly influences the allowed dipole transitions, causing increasing two-pair absorption on the high-energy side of the decreasing one-pair absorption. Surface-polarization effects are studied for quantum dots embedded in another dielectric medium.

Theory of optically excited intrinsic semiconductor quantum dots

A quantitative analysis of carrier-carrier scattering and optical dephasing in semiconductors is presented and results are given for quasiequilibrium situations and for the relaxation of a kinetic hole in a quasithermal carrier distribution. The calculations involve direct numerical integration of the Boltzmann equation for carrier-carrier scattering in the Born approximation. The screening of the Coulomb interaction is treated consistently in the fully dynamical random-phase approximation. Carrier relaxation rates are extracted from the Boltzmann-equation solution and a quantitative test of the relaxation-time approximation for situations near thermal quasiequilibrium is performed. The parametric dependence of carrier-collision rates and dephasing on plasma density, temperature, and electron and hole masses is discussed and analyzed in terms of phase-space blocking and screening.

Carrier-carrier scattering and optical dephasing in highly excited semiconductors.

The coherent interaction of femtosecond laser pulses and thin CdSe and GaAs samples is investigated experimentally and theoretically Oscillatory structures in the differential probe transmission around the exciton resonance and around the pump frequency are observed when the probe pulse precedes the pump Comparison with theory attributes the oscillations to the coherent coupling between the light field and the electron-hole transitions in the semiconductor For nonresonant excitation, the oscillatory structures around the exciton are identified as the early stages of the optical Stark effect

Femtosecond Studies of Coherent Transients in Semiconductors

Femtosecond differential absorption measurements of the quantum-confined transitions in CdSe microcrystallites are reported. Spectral hole burning is observed, which is accompanied by an induced absorption feature on the high-energy side. The spectral position of the burned hole depends on the excitation wavelength. For excitation on the low-energy side of the lowest quantum-confined transition, a slight shift of the hole towards the line center is observed. The hole width increases with pump intensity and the magnitude of the induced transparency saturates at the highest excitation level. The results are consistently explained by bleaching of one-pair states and induced absorption caused by the photoexcited two electron-hole pair states. It is concluded that the presence of one electron in the excited state prevents further absorption of photons at the pair-transition energy and accounts for the major portion of the bleaching of the transition. >

M. Lindberg

Papers

Effective Bloch equations for semiconductors

Theory of optically excited intrinsic semiconductor quantum dots

Carrier-carrier scattering and optical dephasing in highly excited semiconductors.

Femtosecond Studies of Coherent Transients in Semiconductors

Femtosecond optical nonlinearities of CdSe quantum dots